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In situ transmission electron microscopy and spectroscopy studies of interfaces in Li ion batteries: Challenges and opportunities

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Abstract

Transmission electron microscopy (TEM) and spectroscopy have been evolved to a stage such that they can be routinely used to probe the structure and composition of the materials with the resolution of a single atomic column. However, a direct in situ TEM observation of structural evolution of the materials in a lithium ion battery during dynamic operation of the battery has never been reported. In this paper, we report the results of exploring the in situ TEM techniques for observation of interfaces in the lithium ion battery during the operation of the battery. A miniature battery was fabricated using a single nanowire and an ionic liquid electrolyte. The structure and composition of the interface across the anode and the electrolyte was studied using TEM imaging, electron diffraction, and electron energy-loss spectroscopy. In addition, we also explored the possibilities of carrying out in situ TEM studies of lithium ion batteries with a solid state electrolyte.

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References

  1. J.M. Tarascon, M. Armand: Issues and challenges facing rechargeable lithium batteries. Nature414359 (2001)

    Article  CAS  Google Scholar 

  2. R. Dedryvere, H. Martinez, S. Leroy, D. Lemordant, F. Bonhomme, P. Biensan, D. Gonbeau: Surface film formation on electrodes in a LiCoO2/graphite cell: A step by step XPS study. J. Power Sources174462 (2007)

    Article  CAS  Google Scholar 

  3. F. Kong, R. Kostecki, G. Nadeau, X. Song, K. Zaghib, K. Kinoshita, F. McLarnon: In situ studies of SEI formation. J. Power Sources97-9858 (2001)

    Article  CAS  Google Scholar 

  4. H. Bryngelsson, M. Stjerndahl, T. Gustafsson, K. Edstrom: How dynamic is the SEI? J. Power Sources174970 (2007)

    Article  CAS  Google Scholar 

  5. G.Y. Chen, X.Y. Song, T.J. Richardson: Electron microscopy study of the LiFePO4 to FePO4 phase transition. Electrochem. Solid-State Lett.9, (6) A295 (2006)

    Article  CAS  Google Scholar 

  6. S.K. Eswaramoorthy, J.M. Howe, G. Muralidharan: In situ determination of the nanoscale chemistry and behavior of solid-liquid systems. Science3181437 (2007)

    Article  CAS  Google Scholar 

  7. A. Brazier, L. Dupont, L. Dantras-Laffront, N. Kuwata, J. Kawamura, J.M. Tarascon: First cross-section observation of an all solid-state lithium-ion “nanobattery” by tramsmission electron microscopy. Chem. Mater.202352 (2008)

    Article  CAS  Google Scholar 

  8. S.F. Lux, M. Schmuck, B. Rupp, W. Kern, G.B. Appetecchi, S. Passerini, M. Winter, A. Balducci: Mixtures of ionic liquids in combination with graphite electrodes: The role of Li-salt. ECS Transactions16, (35) 45 (2009)

    Article  CAS  Google Scholar 

  9. A. Lewandowski, A. Świderska-Mocek: Properties of the graphite-lithium anode in N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide as an electrolyte. J. Power Sources171, (2) 938 (2007)

    Article  CAS  Google Scholar 

  10. R. Retoux, T. Brousse, D.M. Schleich: High-resolution electron microscopy investigation of capacity fade in SnO2 electrodes for lithium-ion batteries. J. Electrochem. Soc.146, (7) 2472 (1999)

    Article  CAS  Google Scholar 

  11. C. Delmas, M. Maccario, L. Croguennec, F.L. Cras, F. Weill: Lithium deintercalation in LiFePO4 nanoparticles via a Domoni-Cascade model. Nat. Mater.7665 (2008)

    Article  CAS  Google Scholar 

  12. P. Gibot, M. Casas-Cabanas, L. Laffont, S. Levasseur, P. Carlach, S. Hamelet, J.M. Tarascon, C. Masquelier: Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4. Nat. Mater.77741 (2008)

    Article  Google Scholar 

  13. L. Laffont, C. Delacourt, P. Gibot, M.Y. Wu, P. Kooyman, C. Masquelier, J. Marie Tarascon: Study of the LiFePO4/FePO4 two-phase system by high-resolution electron energy loss spectroscopy. Chem. Mater.185520 (2006)

    Article  CAS  Google Scholar 

  14. V. Mauchamp, P. Moreau, L. Moncondut, M.L. Doublet, F. Boucher, G. Ouvrard: Determination of lithium insertion sites in LixTiP4 (x = 2-11) by electron energy-loss spectroscopy. J. Phys. Chem. C1113996 (2007)

    Article  CAS  Google Scholar 

  15. D. Wang, D. Choi, Z. Yang, V.V. Viswanathan, Z. Nie, C.M. Wang, Y. Song, J.G. Zhang, J. Liu: Synthesis and Li ion insertion properties of highly crystalline mesoporous rutile TiO2. Chem. Mater.203435 (2008)

    Article  CAS  Google Scholar 

  16. A. Hightower, C.C. Ahn, B. Fultz, P. Rez: Electron energy-loss spectroscopy on lithiated graphite. Appl. Phys. Lett.77, (2) 238 (2000)

    Article  CAS  Google Scholar 

  17. G. Chen, C. Li, X. Xu, J. Li, U. Kolb: Electronic structure of Li(CO0.7-xAl0.3)MgxO2 studied by electron energy-loss spectroscopy. Appl. Phys. Lett.83, (6) 1142 (2003)

    Article  CAS  Google Scholar 

  18. H. Gabrisch, R. Yazami, B. Fultz: The character of dislocationsin LiCoO2. Electrochem. Solid-State Lett.5, (6) A111 (2002)

    Article  CAS  Google Scholar 

  19. S.I. Nishimura, G. Kobayashi, K. Ohoyama, R. Kanno, M. Yashima, A. Yamada: Experimental visulization of lithium diffusion in LixFePO4. Nat. Mater.7707 (2008)

    Article  CAS  Google Scholar 

  20. A.R. Harutyunyan, G.G. Chen, T.M. Paronyan, E.M. Pigos, O.A. Kuznetsov, K. Hewaparakrama, S.M. Kim, D. Zakharov, E.A. Stach, G.U. Sumanasekera: Preferential growth of single-walled carbon nanotubes with metallic conductivity. Science326, (5949) 116 (2009)

    Article  CAS  Google Scholar 

  21. B.J. Kim, J. Tersoff, S. Kodambaka, M.C. Reuter, E.A. Stach, F.M. Ross: Kinetics of individual nucleation events observed in nanoscale vapor-liquid-solid growth. Science322, (5904) 1070 (2008)

    Article  CAS  Google Scholar 

  22. P.L. Hansen, J.B. Wagner, S. Helveg, J.R. Rostrup-Nielsen, B.S. Clausen, H. Topsoe: Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals. Science295, (5562) 2053 (2002)

    Article  CAS  Google Scholar 

  23. Z.W. Shan, R.K. Mishra, S.A.S. Asif, O.L. Warren, A.M. Minor: Mechanical annealing and source-limited deformation in submicrometre-diameter Ni crystals. Nat. Mater.7, (2) 115 (2008)

    Article  CAS  Google Scholar 

  24. A.M. Minor, S.A.S. Asif, Z.W. Shan, E.A. Stach, E. Cyrankowski, T.J. Wyrobek, O.L. Warren: A new view of the onset of plasticity during the nanoindentation of aluminium. Nat. Mater.5, (9) 697 (2006)

    Article  CAS  Google Scholar 

  25. H.M. Zheng, R.K. Smith, Y.W. Jun, C. Kisielowski, U. Dahmen, A.P. Alivisatos: Observation of single colloidal platinum nanocrystal growth trajectories. Science324, (5932) 1309 (2009)

    Article  CAS  Google Scholar 

  26. M.J. Williamson, R.M. Tromp, P.M. Vereecken, R. Hull, F.M. Ross: Dynamic microscopy of nanoscale cluster growth at the solid-liquid interface. Nat. Mater.2, (8) 532 (2003)

    Article  CAS  Google Scholar 

  27. N. de Jonge, D.B. Peckys, G.J. Kremers, D.W. Piston: Electron microscopy of whole cells in liquid with nanometer resolution. Proc. Natl. Acad. Sci. U.S.A.106, (7) 2159 (2009)

    Article  Google Scholar 

  28. J.X. Wang, D.F. Liu, X.Q. Yan, H.J. Yuan, L.J. Ci, Z.P. Zhou, Y. Gao, L. Song, L.F. Liu, W.Y. Zhou, G. Wang, S.S. Xie: Growth of SnO2 nanowires with uniform branched structures. Solid State Commun.13089 (2004)

    Article  CAS  Google Scholar 

  29. Z.W. Pan, Z.R. Dai, Z.L. Wang: Nanobelts of semiconducting oxides. Science2911947 (2001)

    Article  CAS  Google Scholar 

  30. I.A. Courtney, J.R. Dahn: Electrochemical and in situ x-ray diffraction studies of the reaction of lithium with tin oxide composites. J. Electrochem. Soc.1442045 (1997)

    Article  CAS  Google Scholar 

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Wang, C.M., Xu, W., Liu, J. et al. In situ transmission electron microscopy and spectroscopy studies of interfaces in Li ion batteries: Challenges and opportunities. Journal of Materials Research 25, 1541–1547 (2010). https://doi.org/10.1557/JMR.2010.0198

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  • DOI: https://doi.org/10.1557/JMR.2010.0198

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